JPH10194883A - Coated granular fertilizer - Google Patents
Coated granular fertilizerInfo
- Publication number
- JPH10194883A JPH10194883A JP8356798A JP35679896A JPH10194883A JP H10194883 A JPH10194883 A JP H10194883A JP 8356798 A JP8356798 A JP 8356798A JP 35679896 A JP35679896 A JP 35679896A JP H10194883 A JPH10194883 A JP H10194883A
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic polyester
- fertilizer
- granular fertilizer
- coated
- aliphatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Fertilizers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は粒状肥料を、生分解
性を有する特定の脂肪族ポリエステルを用いて被覆して
なる被覆粒状肥料に関するものである。TECHNICAL FIELD The present invention relates to a coated granular fertilizer obtained by coating a granular fertilizer with a specific aliphatic polyester having biodegradability.
【０００２】[0002]
【従来の技術】化学肥料は本質的に水溶性であるため、
散水，雨水等により溶出し、長期にわたってその効果を
持続することが困難である。従来より施肥の省力化のた
めに、一度の施肥で長期間効果を持続することができる
緩効性肥料が注目されている。肥料に緩効性を持たせる
手段としては、肥料をマトリックスとしてのアスファル
ト等の難水溶性物質と混合・成形し徐放性を付与したも
の、ポリオレフィン等の合成樹脂で肥料を被覆すること
により徐放性を付与したもの等があるが、何れも肥料以
外の物質が土壌中で分解せず、土壌の安全面からの懸念
がある。BACKGROUND OF THE INVENTION Because fertilizers are essentially water-soluble,
It is eluted by water spray, rain water, etc., and it is difficult to maintain its effect for a long period of time. Conventionally, for the purpose of labor saving of fertilizer, slow-release fertilizers that can maintain the effect for a long time with one fertilization have been attracting attention. Means of imparting a slow release effect to fertilizers include mixing and forming the fertilizer with a poorly water-soluble substance such as asphalt as a matrix to impart sustained release, or gradually covering the fertilizer with a synthetic resin such as polyolefin. Although there is a substance to which release is given, substances other than fertilizer are not decomposed in soil, and there is a concern from the viewpoint of soil safety.
【０００３】また、上記の懸念を払拭すべく、生分解性
の高分子物質を被覆材料に用いて徐放性を付与した被覆
肥料が種々報告されている。しかし、従来の生分解性高
分子化合物は機械的物性が劣り、肥料の製造，搬送，保
存の間に被覆層に亀裂ができやすく、期待される肥料の
徐放性が損なわれるものが多かった。[0003] Further, in order to eliminate the above-mentioned concerns, various coated fertilizers have been reported in which a biodegradable polymer substance is used as a coating material to impart sustained release. However, conventional biodegradable polymer compounds have poor mechanical properties, tend to crack the coating layer during the production, transportation and storage of fertilizers, often impairing the expected sustained release of fertilizers. .
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、肥料の放出期間が十分に長く、運搬，保存
の間に肥料の放出期間が短くならず、かつ分解しない物
質により農地を汚染することがない被覆粒状肥料を提供
することである。The problem to be solved by the present invention is that the release period of the fertilizer is sufficiently long, the release period of the fertilizer does not become short during transportation and storage, and the agricultural land is not decomposed. It is to provide a coated granular fertilizer that does not contaminate.
【０００５】[0005]
【課題を解決するための手段】本発明者らは鋭意検討し
た結果、特定の脂肪族ポリエステルを使用して被覆を行
うことにより、上記課題を解決できることを見出した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by coating with a specific aliphatic polyester.
【０００６】すなわち、本発明は、被覆肥料、及びその
表面を被覆している次式〔Ｉ〕で表わされる少なくとも
２つのウレタン結合を含む脂肪族ポリエステルを含む被
覆粒状肥料である。That is, the present invention is a coated fertilizer, and a coated granular fertilizer containing an aliphatic polyester having at least two urethane bonds represented by the following formula [I] and covering the surface thereof.
【０００７】[0007]
【化２】 （式中、Ｒ1 は炭素数２〜１０のアルキレン基であり、
Ｒ2 は炭素数２〜１２のアルキレン基であり、Ｒ3 はジ
イソシアナートの残基であり、ｍ≧３０、Ｍ≧１であ
る）。Embedded image (Wherein, R 1 is an alkylene group having 2 to 10 carbon atoms,
R 2 is an alkylene group having 2 to 12 carbon atoms, R 3 is a residue of diisocyanate, and m ≧ 30 and M ≧ 1).
【０００８】[0008]
【発明の実施の形態】上記のウレタン結合を含む脂肪族
ポリエステルにおける脂肪族ポリエステル部は、脂肪族
ジオールと脂肪族ジカルボン酸（又はジカルボン酸エス
テル）を重合させることにより得られる。かかる脂肪族
ポリエステル自体の製造法自体は公知である（特開平8-
109248）。コハク酸１モルに対して小過剰（たとえば
１．０５〜１．３モル）の１，４−ブタンジオールを用
いることにより、生成するポリエステルの両末端のほと
んどはヒドロキシル基である。脂肪族ポリエステルの数
平均分子量は、好ましくは１５，０００以上である。BEST MODE FOR CARRYING OUT THE INVENTION The aliphatic polyester moiety in the above aliphatic polyester containing a urethane bond can be obtained by polymerizing an aliphatic diol and an aliphatic dicarboxylic acid (or dicarboxylic acid ester). A method for producing such an aliphatic polyester itself is known (Japanese Unexamined Patent Publication No.
109248). By using a small excess (for example, 1.05 to 1.3 mol) of 1,4-butanediol relative to 1 mol of succinic acid, most of both ends of the resulting polyester are hydroxyl groups. The number average molecular weight of the aliphatic polyester is preferably 15,000 or more.
【０００９】脂肪族ジオールは、炭素数２〜１０のジオ
ールであり、たとえばエチレングリコール、１，４−ブ
タンジオール、１，６−ヘキサンジオール、１，２−プ
ロパンジオール、１，３−プロパンジオール、１，３−
ブタンジオール、１，５−ペンタンジオール、３−メチ
ル−１，５−ペンタンジオール、１，７−ヘプタンジオ
ール、１，８−オクタンジオール、１，９−ノナンジオ
ール、１，１０−デカンジオール、ネオペンチルグリコ
ール等が挙げられる。これらの中で、エチレングリコー
ル、１，４−ブタンジオール、１，６−ヘキサンジオー
ルが、粒状肥料のための優れた被覆を与えるので好まし
い。上記脂肪族グリコールは、単独で用いても良くまた
二種以上を混合して用いても良い。The aliphatic diol is a diol having 2 to 10 carbon atoms, such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-propanediol, 1,3-
Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neo Pentyl glycol and the like. Of these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol are preferred because they provide an excellent coating for granular fertilizers. The aliphatic glycols described above may be used alone or as a mixture of two or more.
【００１０】脂肪族ジカルボン酸は、炭素数２〜１２の
ジカルボン酸であり、たとえばコハク酸、アジピン酸、
ドデカンジカルボン酸、シュウ酸、マロン酸、グルタル
酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン
酸、ノナンジカルボン酸等を挙げることができる。脂肪
族ジカルボン酸のジエステルとしては、上記酸とＣ1〜
Ｃ4 の低級アルコールとのジエステルが好ましい。The aliphatic dicarboxylic acid is a dicarboxylic acid having 2 to 12 carbon atoms, such as succinic acid, adipic acid,
Dodecanedicarboxylic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid and the like can be mentioned. As the diester of the aliphatic dicarboxylic acid, the above acid and C 1 to
Diesters of lower alcohols C 4 are preferred.
【００１１】得られた脂肪族ポリエステルを加熱溶融
し、これにジイソシアナートを添加混合すると、目的と
する少くとも２つのウレタン結合を含む脂肪族ポリエス
テルが得られる。ジイソシアナートとしては、２，４−
トリレンジイソシアナート、２，４−トリレンジイソシ
アナートと２，６−トリレンジイソシアナートとの混合
体、ジフェニルメタンジイソシアナート、１，５−ナフ
チレンジイソシアナート、キシリレンジイソシアナー
ト、水素化キシリレンジイソシアナート、ヘキサメチレ
ンジイソシアナート、イソホロンジイソシアナートが挙
げられ、ヘキサメチレンジイソシアナートが好ましい。
ジイソシアナートの添加量は、好ましくはポリエステル
１００重量部に対して０．１〜５重量部、特に０．５〜
３重量部である。０．１重量部未満では、反応が不十分
であり、５重量部を超えると、ゲル化が発生し易くな
る。The resulting aliphatic polyester is heated and melted, and a diisocyanate is added thereto and mixed to obtain the desired aliphatic polyester containing at least two urethane bonds. As the diisocyanate, 2,4-
Tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate Examples include isocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, with hexamethylene diisocyanate being preferred.
The amount of diisocyanate added is preferably 0.1 to 5 parts by weight, particularly 0.5 to 100 parts by weight of polyester.
3 parts by weight. If the amount is less than 0.1 part by weight, the reaction is insufficient, and if it exceeds 5 parts by weight, gelation is liable to occur.
【００１２】本発明において、Ｒ1 がテトラメチレン基
であり、Ｒ2 がジメチレン基であり、Ｒ3 がヘキサメチ
レン基である場合に、本発明の目的にかなう特に優れた
粒状肥料用の被覆が達成されることが判った。In the present invention, when R 1 is a tetramethylene group, R 2 is a dimethylene group and R 3 is a hexamethylene group, a particularly excellent coating for granular fertilizer meeting the object of the present invention is provided. It turned out to be achieved.
【００１３】上記のウレタン結合を有する脂肪族ポリエ
ステルの数平均分子量は、好ましくは３０，０００以
上、特に３０，０００〜３００，０００である。The above-mentioned aliphatic polyester having a urethane bond has a number average molecular weight of preferably 30,000 or more, particularly 30,000 to 300,000.
【００１４】ウレタン結合を有する脂肪族ポリエステル
を粒状肥料に被覆する方法自体は、特に限定されない。
たとえば該ポリエステルを溶剤に溶解又は分散させ、浮
遊または流動状態にある粒状肥料に施与し（好ましくは
噴霧し）、次に溶剤を揮発させることができる。粒状肥
料を噴流層の状態にし、その中にポリエステルの溶液又
は分散液を噴霧し、かつ必要により噴流層を高められた
温度に保つ方法が、良好な被覆を効率的に与える故に好
ましい。溶剤としては、クロロホルム、ジクロロベンゼ
ン、トリクロロベンゼン、テトラクロロベンゼン、塩化
メチレン、クロロフェノール、Ｎ−メチルピロリドン等
を用いることができ、しかし、これらに限定されない。
該ポリエステルと共に、他のポリマー、例えばポリオレ
フィン、スチレン（共）重合体、ビニル系重合体、ジエ
ン系ゴム等を併用することもできる。The method of coating the granular fertilizer with the aliphatic polyester having a urethane bond is not particularly limited.
For example, the polyester can be dissolved or dispersed in a solvent, applied to a particulate fertilizer in a floating or fluid state (preferably sprayed), and then the solvent can be volatilized. A method in which the granular fertilizer is in the form of a spouted bed, in which a solution or dispersion of the polyester is sprayed, and where necessary, the spouted bed is maintained at an elevated temperature is preferred for efficiently providing good coating. As the solvent, chloroform, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, methylene chloride, chlorophenol, N-methylpyrrolidone and the like can be used, but are not limited thereto.
Along with the polyester, other polymers such as polyolefin, styrene (co) polymer, vinyl polymer, diene rubber and the like can be used in combination.
【００１５】粒状肥料に対して５〜１０重量％の上記ポ
リエステルが被覆として存在することが好ましい。下限
未満では、十分な徐放性を有しながら亀裂が少ない被覆
を与えることが困難である。上限を超えると、コスト高
になる。It is preferred that 5 to 10% by weight of the above-mentioned polyester is present as a coating, based on the granular fertilizer. If the amount is less than the lower limit, it is difficult to provide a coating having sufficient sustained-release properties and less cracks. Exceeding the upper limit increases costs.
【００１６】[0016]
【実施例】以下の実施例で、本発明を更に詳しく説明す
るが、本発明はかかる実施例に限定されるものではな
い。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１７】実施例１ 脂肪族ポリエステルの製造： （１）撹拌機、リービッヒコンデンサー、温度計、窒素
導入口を備えた３ｌの反応器に、コハク酸（ＳＡ）５９
０．５ｇ、１，４−ブタンジオール（ＢＤＯ）５４３．
４ｇ、ヒドロキノンモノメチルエーテル（ＨＱＭＭＥ）
１４０mgを入れ、反応器内の窒素置換を十分行った。そ
の後、窒素気流中で激しく撹拌しつつ、反応温度を徐々
に２００℃まで上昇させ、３時間エステル化反応を行っ
た。（２）その後、ゆっくりと１Torrまで減圧して、２
００℃で１時間反応させた。（３）チタンテトライソプ
ロポキシド１．４２１mgを添加し、２２０℃、０．１To
rrで５時間重縮合反応を行った。一旦この時点で生成し
たポリマーを少量サンプリングした。Example 1 Production of Aliphatic Polyester: (1) Succinic acid (SA) 59 was placed in a 3 liter reactor equipped with a stirrer, a Liebig condenser, a thermometer and a nitrogen inlet.
0.5 g, 1,4-butanediol (BDO) 543.
4 g, hydroquinone monomethyl ether (HQMME)
140 mg was charged, and the inside of the reactor was sufficiently purged with nitrogen. Thereafter, the reaction temperature was gradually increased to 200 ° C. with vigorous stirring in a nitrogen stream to carry out an esterification reaction for 3 hours. (2) Then, slowly reduce the pressure to 1 Torr,
The reaction was performed at 00 ° C. for 1 hour. (3) 1.421 mg of titanium tetraisopropoxide was added, and the mixture was heated at 220 ° C. for 0.1
A polycondensation reaction was performed at rr for 5 hours. A small amount of the polymer once formed at this point was sampled.
【００１８】ポリマーの分析：得られた白色の樹脂のＭ
ｎ，Ｍｗを、ゲルパーミエーションクロマトグラフィー
（ＧＰＣ）により求めた。ＧＰＣの条件は下記のとおり
である。なお、分子量はポリスチレン（ＰＳ）換算で求
めた。Analysis of polymer: M of white resin obtained
n and Mw were determined by gel permeation chromatography (GPC). The conditions of GPC are as follows. The molecular weight was determined in terms of polystyrene (PS).
【００１９】 使用機種 ：ＬＣ９Ａ（島津製作所製） 溶媒 ：クロロホルム 溶媒流速 ：０．５ml／min 試料濃度 ：４mg／ml カラム ：ＴＳＫgel Ｇ５０００ＨHR＋Ｇ３０００Ｈ
HR（東ソー株式会社）（７．８mm内径×３０cm） カラム温度：４０℃ 分子量スタンダード：ポリスチレン Ｍｎ＝１９，０００かつＭｗ＝４７，０００であった。Model used: LC9A (manufactured by Shimadzu Corporation) Solvent: chloroform Solvent flow rate: 0.5 ml / min Sample concentration: 4 mg / ml Column: TSKgel G5000H HR + G3000H
HR (Tosoh Corporation) (7.8 mm inner diameter × 30 cm) Column temperature: 40 ° C. Molecular weight standard: polystyrene Mn = 19,000 and Mw = 47,000.
【００２０】ウレタン化反応：前記のポリエステル５４
０ｇを２１０℃に熔融した状態で撹拌しながら、ヘキサ
メチレンジイソシアナート７ｇを添加した。熔融粘度は
急激に上昇したが、ゲル化は生じなかった。前記ポリマ
ーの分析と同条件でＧＰＣを測定した結果、Ｍｎ＝３
６，６００、Ｍｗ＝１７８，０００であった。また、Ｍ
ＦＲ（１９０℃、荷重２．１６kg）を測定したところ、
１．６ｇ／１０分であった。Urethane-forming reaction: The above-mentioned polyester 54
While stirring 0 g at 210 ° C., 7 g of hexamethylene diisocyanate was added. The melt viscosity rose sharply, but no gelling occurred. As a result of measuring GPC under the same conditions as in the analysis of the polymer, Mn = 3
6,600, Mw = 178,000. Also, M
When the FR (190 ° C., load 2.16 kg) was measured,
It was 1.6 g / 10 minutes.
【００２１】被覆：塔径が１０cmの噴流被覆装置に平均
粒径３．３mmの尿素肥料を仕込み、下部より６０ｍ3 ／
時間で熱風を送り、噴流撹拌を起こしながら内部温度を
６０℃に上昇させた。上記で得たポリマーを濃度３wt％
となるようにクロロホルムに溶解させ（液温は６０
℃）、この溶液を噴流被覆装置下部の熱風吹出し口に設
けられた二流体ノズルより噴霧し、粒状肥料上に被膜を
形成した。被覆量は、尿素肥料重量に対して約８重量％
であった。Coating: A urea fertilizer having an average particle diameter of 3.3 mm was charged into a jet coating apparatus having a tower diameter of 10 cm, and 60 m 3 /
The internal temperature was raised to 60 ° C. while hot air was sent for a period of time to cause jet stirring. Concentration of polymer obtained above is 3wt%
And dissolved in chloroform (solution temperature is 60
° C), the solution was sprayed from a two-fluid nozzle provided at the hot air outlet at the bottom of the jet coating device to form a film on the granular fertilizer. Coating amount is about 8% by weight based on the weight of urea fertilizer
Met.
【００２２】溶出試験：得られた被覆粒状肥料の一定量
をポリエステル製の網に入れ、２５℃の温水中に吊るし
た。一定期間（３０日，６０日，９０日）密閉放置した
後（液温は２５℃に保持）、水中の窒素を測定した。Dissolution test: A certain amount of the obtained coated granular fertilizer was put in a polyester net and suspended in warm water at 25 ° C. After leaving the container tightly closed for a certain period of time (30 days, 60 days, 90 days) (the liquid temperature was kept at 25 ° C.), nitrogen in the water was measured.
【００２３】実施例２ ポリマーの被覆量を約１２％とした以外は、実施例１と
同様に行った。Example 2 The procedure of Example 1 was repeated except that the amount of the polymer was about 12%.
【００２４】比較例１ ポリマーの被覆量を約４％とした以外は、実施例１と同
様に行った。Comparative Example 1 The procedure of Example 1 was repeated, except that the amount of the polymer was about 4%.
【００２５】比較例２ 実施例１と同様にして脂肪族ポリエステルを作り、しか
し続くウレタン化反応を行なわず、脂肪族ポリエステル
を用いて実施例１と同様に被覆をした。Comparative Example 2 An aliphatic polyester was prepared in the same manner as in Example 1, but was coated in the same manner as in Example 1 using the aliphatic polyester without performing the subsequent urethanization reaction.
【００２６】結果を表１に示す。The results are shown in Table 1.
【００２７】[0027]
【表１】 実施例１及び２においては、初期の肥料の溶出が少な
い。光学顕微鏡での観察によると、被覆には亀裂が少な
い。比較例１においては、肥料の初期の溶出が多い。被
覆の量が少なすぎたので、亀裂が多数あり、また被覆が
不完全で肥料粒子の一部分が露出していたためであると
考えられる。[Table 1] In Examples 1 and 2, initial elution of fertilizer is small. According to observation with an optical microscope, the coating has few cracks. In Comparative Example 1, the initial elution of the fertilizer was large. It is considered that the amount of the coating was too small, so there were many cracks, and the coating was incomplete and a part of the fertilizer particles was exposed.
【００２８】一方、ウレタン結合を有していない脂肪族
ポリエステルを用いた比較例２においては、被覆に亀裂
が多く、肥料の初期溶出が多い。ここでは噴流層を用い
て被覆を行ったが、より緩やかな状態で被覆を行うこと
により、比較例２の脂肪族ポリエステルを用いた場合に
でも製造直後の亀裂を少なくできる。しかし、搬送，保
管，散布等の間に機械力，温度ストレス等がかかると、
比較例２のものは亀裂が生じやすい。On the other hand, in Comparative Example 2 using an aliphatic polyester having no urethane bond, the coating had many cracks and the initial elution of fertilizer was large. Here, coating was performed using a spouted bed. However, by performing coating in a gentler state, cracks immediately after production can be reduced even when the aliphatic polyester of Comparative Example 2 is used. However, when mechanical force, temperature stress, etc. are applied during transportation, storage, spraying, etc.,
In the case of Comparative Example 2, cracks are easily formed.
【００２９】[0029]
【発明の効果】肥料の放出期間が十分に長く、搬送，保
管，散布の間に放出期間が短くならず、かつ分解しない
物質により農地を汚染することがない緩効性の被覆粒状
肥料が得られた。The release period of the fertilizer is sufficiently long, the release period is not short during transportation, storage and application, and a slow-acting coated granular fertilizer is obtained which does not pollute the agricultural land with substances that do not decompose. Was done.
【化３】 Embedded image
Claims (4)
次式〔Ｉ〕で表わされる少なくとも２つのウレタン結合
を含む脂肪族ポリエステルを含む被覆粒状肥料 【化１】 （式中、Ｒ1 は炭素数２〜１０のアルキレン基であり、
Ｒ2 は炭素数２〜１２のアルキレン基であり、Ｒ3 はジ
イソシアナートの残基であり、ｍ≧３０、Ｍ≧１であ
る）。1. A coated granular fertilizer comprising a coated fertilizer and an aliphatic polyester containing at least two urethane bonds represented by the following formula [I] and covering the surface thereof: (Wherein, R 1 is an alkylene group having 2 to 10 carbon atoms,
R 2 is an alkylene group having 2 to 12 carbon atoms, R 3 is a residue of diisocyanate, and m ≧ 30 and M ≧ 1).
ジメチレン基でありＲ3 がヘキサメチレン基である請求
項１の被覆粒状肥料。2. The coated granular fertilizer according to claim 1, wherein R 1 is a tetramethylene group, R 2 is a dimethylene group, and R 3 is a hexamethylene group.
合が５重量％以上１０重量％以下である請求項１又は２
記載の被覆粒状肥料。3. The method according to claim 1, wherein the ratio of the polyester to the coated fertilizer is 5% by weight or more and 10% by weight or less.
A coated granular fertilizer according to the above.
が、少なくとも３０，０００である請求項１〜３のいず
れか１つに記載の被覆粒状肥料。4. The number average molecular weight Mn of the polyester
Is at least 30,000. The coated granular fertilizer according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8356798A JPH10194883A (en) | 1996-12-27 | 1996-12-27 | Coated granular fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8356798A JPH10194883A (en) | 1996-12-27 | 1996-12-27 | Coated granular fertilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10194883A true JPH10194883A (en) | 1998-07-28 |
Family
ID=18450830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8356798A Pending JPH10194883A (en) | 1996-12-27 | 1996-12-27 | Coated granular fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10194883A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277429A (en) * | 2006-04-07 | 2007-10-25 | Chisso Asahi Hiryo Kk | Polyol, polyurethane coating film and coated granular plant active substance |
-
1996
- 1996-12-27 JP JP8356798A patent/JPH10194883A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277429A (en) * | 2006-04-07 | 2007-10-25 | Chisso Asahi Hiryo Kk | Polyol, polyurethane coating film and coated granular plant active substance |
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